KR101042057B1 - Homogeneous liquid compositions comprising saccharide and oil - Google Patents

Abstract

The present invention provides a composition comprising: a) at least one oil component; b) at least one sugar, in particular liquid sugar solution (LS); And c) an oil based emulsifying concentrate comprising liquid saccharides comprising at least one nonionic surfactant. The concentrate may also contain d) at least one surfactant hydrocarbyl saccharide; Or e) at least one anionic surfactant; Or f) one or more additional oil-soluble nonionic surfactants. The concentrate is typically homogenized for at least 24 hours and easily emulsified by dilution with water. The concentrate may also contain antifoams, in particular polysiloxanes. The emulsion formed by diluting the concentrate in water is applied to the substrate in combination with agrochemical active ingredients, preferably in the form of soluble salts, for weed control.

Self-emulsifying oil, pesticide concentrate composition, weed control

Description

HOMOGENEOUS LIQUID COMPOSITIONS COMPRISING SACCHARIDE AND OIL}

Pesticide compositions have been used to improve the quality and quantity of farm products. In this regard, the pesticide composition enhances biological activity and can act as a nutrient, growth regulator and / or insect repellent, for example herbicides, insecticides, fungicides or tick repellents. However, because such pesticide compositions are expensive to manufacture and sell, it is desirable to improve their effectiveness in unit areas treated with pesticides, thereby reducing the overall cost of use.

In order to enhance or enhance the effectiveness of many pesticides, certain substances are added to an aqueous agricultural spray mixture containing pesticides and simultaneously added to agricultural substrates. Such materials are commonly identified as agricultural spray aids and exist in a wide variety of forms and compositions currently used in commercial farming. The adjuvant products are used to provide a wide range of effects in typical applications, including but not limited to modification of agricultural spray mixtures for controlling foaming, improving the effectiveness of certain pesticides, and / or improving stability or controlling spray droplet diameter. .

In the United States, the most economically beneficial adjuvant products used to enhance or enhance the efficacy of pesticides, primarily insect repellents, are supplied in liquid form. Preferred liquid adjuvant products, both manufactured and sold in the United States (both convenience and economics), are supplied as concentrated liquids and fall into two main categories. These categories include (1) self-emulsifying oil and surfactant compositions more commonly identified as Crop Oil Concentrates (COC), and (2) concentrated liquid nonionic surfactants (Non-Ionic Surfactants, Surfactants which are readily dissolved or dispersed in water known as NIS). Commercial distribution channels in the United States effectively carry large volumes of these products in large quantities effectively, making COC and NIS type products very economical for their intended use. By combining the more expensive insect repellents with economically beneficial, primarily low cost adjuvant products in the spray mixture, the efficacy of the insect repellents can be improved, thereby improving the overall economics of commercial agriculture. The use of an effective adjuvant product in this way can reduce the seasonal cost of producing agricultural commodities and also improve the product yield to provide economic benefits to those who use it.

One of the largest single groups of such effective liquid adjuvant products sold in the United States is COC compositions containing 60 to 90% (volume) of suitable agricultural grade inorganic oils, and other forms of this adjuvant type are vegetable oils or methylated seed oils. It contains. All commercially important forms of this adjuvant type include oil soluble surfactant compositions consisting of blends of anionic and / or nonionic surfactants that provide self-emulsification of oil components upon dilution in aqueous agricultural spray mixtures. And total surfactant concentration in conventional COC products may range from 1 to 40%, most typically 10 to 17%.

Although the oil and surfactant compositions in the COC adjuvant product may be provided in a preemulsified system in water (oil-in-water emulsion), the additional production cost for the emulsified adjuvant product is There is a tendency to make the system economically less beneficial than the equivalent volume of oil aid provided as COC. Aqueous systems are also generally more complex to develop and manufacture, due to the tendency of aqueous emulsions to sustain microbial growth, foam, settle / settle, and degrade over time or during freeze-thaw cycles. , An undesirable feature that requires separate thickening, preservation and the use of an anti-freezing system. Including water as the dispersion medium also dilutes the active ingredient (oil and surfactant composition), making it more expensive to deliver the system to the rice fields based on one pound of "active" adjuvant. Logical costs also increase based on this if more water is delivered than could otherwise be present in similar COC type systems.

Recently, there have been certain improvements in the cost-effectiveness of these economically beneficial crop oil concentrates. Most of these improvements were focused on two aspects of the composition. The first aspect is to increase the total concentration of oil-soluble surfactant emulsifiers to change the preferred surfactant concentration from 12 to 17% 10 years ago to approximately 40% now, which results in a decrease in the amount of COC adjuvant product added per unit area. Results in improving the cost properties of the supplements. The second aspect is the selection of a specific surfactant type based on both field data and scientific judgment, and this change is related to the improvement of the performance of the adjuvant product with the specific parasitic product. PCT Publication No. WO 95 03881 to Auda et al. Describes agrochemical crop oils containing oil (s), hydrocarbyl saccharide surfactants, and additional nonionic surfactants that are easily emulsified upon dilution with water. Concentrates are disclosed. The COC adjuvant composition is associated with enhanced or enhanced weed control performance with soluble salts of N-phosphonomethylglycine.

More recently, Penner's US Pat. No. 5,945,377 discloses compositions incorporating monosaccharides, especially fructose, as a reinforcing herbicide and a herbicide to weeds without reducing the resistance of crops to herbicides. The composition is used as a propellant in water in the weed extinction method. Although not considering NIS supplements, corn syrup was evaluated as a supplement with various post-germination herbicides in greenhouse and field studies. The biggest improvement in herbicide activity is an effective nonionic adjuvant with high concentrations of fructose corn syrup added with ammonium sulphate and anionic herbicides such as glyphosate and glufosinate for the control of grass species such as fall ragweed. Was observed. The efficacy of corn syrup as an adjuvant is specific to both weeds and herbicides.

The publication (WO 95 03881) discloses the self dispersion of alkylpolysaccharide surfactants in crop oil concentrates (COCs). The composition does not include the additional aqueous liquid non-surfactant polysaccharide component recently found to promote the herbicidal activity of glyphosate. Total surfactant concentrations (approximately from 10 to 10) that are similar to those currently used are powerful single phase compositions containing (1) an oil adjuvant, (2) a sugar adjuvant, and (3) an optimal amount of surfactant, with a corresponding minimum amount of additional water. It was concluded that it is possible to deliver a liquid agricultural supplement product highly concentrated to 40% w / w). Successful incorporation of an effective sugar adjuvant without expensive can improve the cost-effectiveness of the final adjuvant product. The product obtained is commercially beneficial to the manufacturer and economically beneficial to the purchaser / user. Another advantage when mixing the sugar and surfactant adjuvant compositions with conventional COC adjuvant compositions is that significant gains can be obtained by providing a very broadly effective adjuvant composition having the desired characteristics of COC, NIS and newer sugar adjuvant types. It may be a commercial advantage.

The compositions described are intended as commercial alternatives to conventional 17 and 40% surfactants in oil based COC auxiliaries used in the agricultural market. This type of COC adjuvant is cost effective for use with most water-dispersible pesticides, but represents the most commercially available parasiticide in the United States, resulting in conventional glyphosate with the largest single advocate sales opportunities. It is not the most effective type of adjuvant for the soluble salt of N-phosphonomethylglycine called. The most effective NIS adjuvants (identified as ethoxylated tallow alkylamines) for use with glyphosate are now typically combined with concentrated glyphosate solution products, making them easy to use as adjuvant products for incorporation into agricultural spray mixtures. Cannot be used. With the expiration of the patent for concentrated glyphosate salt solution products, other forms of products, including products that do not knowingly contain NIS adjuvants, which are preferred as a means to reduce the cost of formulated glyphosate and to increase the concentration in the solution product thereof. Insect repellents have also become available. It would be advantageous to demonstrate improved potency enhancement of glyphosate products by modifying conventional COC products or COC products described in WO 95 03881 and would be highly desirable as a means to broaden the market for high cost-effective COC adjuvant products.

Ideally acts as both a combinatorial COC adjuvant self-emulsifier and a compatibilizer / stabilizer for the saccharide component, as well as capable of stabilizing and self-emulsifying the oil alone (without the saccharide component), as well as It is desirable to obtain a surfactant composition with particular advantages in providing improved cost savings in purchase and enabling flexible preparation of the COC adjuvant in the same surfactant composition with and without the added liquid sugar component. Do. In addition, since corn syrup aids require simultaneous application of nonionic surfactant aids for optimal performance, a direct combination of oil and corn syrup with a single surfactant system that "activates" sugars and co-emulsifies oil components It will have great economic and competitive advantages. In essence, by using the combined COC and sugar NIS product concepts, the composition will be 100% active at the minimum total concentration of surfactant composition required for optimal performance. Since the surfactant constitutes the most expensive input in the preparation of the component purchase cost (per pound) basis, it is most desirable to reduce the surfactant to the minimum amount required for optimal activity.

The greatest difficulty in the development of combinatorial sugar COC adjuvant products is to enable the formation of homogeneous compositions that function as strong stabilizers for highly concentrated liquid saccharide solutions in oil adjuvant and to provide the required dilution self-emulsification. That is the identification of a suitable surfactant system. These two opposite effects must be provided for one adjuvant product with a minimum amount of total surfactant. Preferably foam modifiers will also be included in the composition.

Wong, US Pat. No. 5,885,646, describes a nut spread having a sugar level of about 15 to about 50%, particularly a flavor nut spread having such a relatively high level of sugar. The substantially homogeneous blend is a fluid suspension based on a homogeneous mixture of lecithin as a surfactant for improving the flowability of sugars, liquid oils, and suspensions, ie nut solid-containing mixtures, and preferably flavors added to the fluid suspension. It is prepared from the agent. The resulting flavor nut spread is more fluid and softer than the product made without using a fluid suspension. This invention does not provide the properties of liquid product homogeneity or self-emulsification, and demonstrates a relatively high viscosity which makes it irrelevant to the invention.

Lyall, US Pat. No. 3,959,498, describes a one-step method of applying sugars and edible fats or oils to a cereal base. No separate step of spraying the oil onto the grain substrate is necessary. The present invention also provides an emulsion grain coating and a method for producing the coating for achieving the above object. A predetermined amount of emulsifier (0.5 to 5%) is added to the aqueous solution of sugar (60 to 85% solids) with a predetermined amount of edible fat or oil or other edible oil- or fat-derived oily substance (5 to 32%). To prepare a syrup emulsion having a water content of 9% to 34% by weight. Edible fats or oils and emulsifiers are added to the aqueous syrup at temperatures ranging from 115 ° F. to 155 ° F. (after emulsifying at 46.1 ° C. to 68.3 ° C., the mixture is heated to about 180 ° F. (82.2 ° C.)). As in the above example, this invention does not provide the properties of liquid product homogeneity or self-emulsification, and demonstrates a relatively high viscosity which makes it irrelevant to the invention. In addition, it provides an oil-in-water emulsion, while the composition claimed herein is a liquid homogeneous (solution or microemulsion) product.

<Overview of invention>

The present invention relates to the development of low temperature (0 ° C.), room temperature (about 20-25 ° C.) and high temperature (eg about 50 ° C.) stabilization systems comprising a mixture of concentrated liquid sugar products and agricultural spray oil. This mixture maintains a homogeneous liquid in the temperature range of about 0 ° C. to 50 ° C. and self-disperses upon dilution in oil. The homogeneous liquids described herein contain surfactants in amounts of 0.5 to 50% by weight, the ratio of oil to sugar products is from 1: 100 to 100: 1, preferred compositions are from 1:10 to 10: 1, more preferred compositions are 1: 3 to 3: 1, most preferred compositions are 1: 2 to 2: 1.

The present invention provides one or more surfactants for delivering stable water dispersible and homogeneous (solution or microemulsion) delivery systems for biologically potent oils, liquid sugar products (primarily concentrated viscous water based syrups), and agricultural adjuvants. Contains the basic ingredients of One particular surfactant composition or surfactant chemistry type is not universally required, and a wide range of surfactant compositions have been developed that can deliver the described products using an understanding of advanced interactions.

Surfactant compositions used to develop such agents include, but are not limited to, alkylpolysaccharides, phosphate esters, sorbitan esters, mono- and diglycerides, polysorbates and ethoxylated alkylamines. A small amount of water may be used to commercialize the oil: surfactant: saccharide system, otherwise it may be commercialized by adding at least 25% water. Surfactant systems that provide the desired homogeneity and compatibility are typically used in the range of 10-40%, more preferred compositions contain 10-35%, and most preferred compositions contain 10-25%.

Preferably the surfactant comprises a nonionic surfactant and is most preferably made completely of at least one nonionic surfactant. If desired, other surfactants can be used, such as one or more anionic surfactants such as anionic alkanolamine salts.

The present invention relates to surfactant compositions and, in particular, to compositions containing a plurality of surfactants and at least one oil, which are easily emulsifiable in water.

The present invention provides a concentrated composition comprising a) at least one oil component, b) at least one non-surfactant saccharide, and c) at least one non-ionic surfactant.

The composition also comprises at least one of d) at least one surfactant hydrocarbyl saccharide, or e) at least one anionic surfactant, or f) at least one additional oil soluble non-ionic surfactant. It may include.

The compositions of the present invention are generally obtained in the form of oil-formulated concentrates which are homogeneous for at least 24 hours and are easily emulsified in water upon dilution. It will be used as a precursor that is diluted in water in agricultural spray mixtures containing pesticides. The spray mixture will contain one or more pesticidal active ingredients and / or nutrients.

The concentrated composition may also include a water miscible liquid, which may be desirable if the viscosity of the composition is inappropriately high. The liquid may comprise water or may be water. The water content is preferably low enough to be homogeneously present for at least 24 hours after the composition is formed. The components and fractions thereof are preferably selected such that any component is readily available only as an aqueous solution, such as HFCS (high fructose corn syrup), and compositions prepared by combining the composition components are stable even if infused with water. . If the concentrate composition comprises water, the concentrate may generally be a water-in-oil solution, a water soluble surfactant combination, or a water-in-oil colloid emulsion or microemulsion in which the water is dispersed in very fine droplets to make the composition clear or transparent. .

The oil component generally has a boiling point of at least about 200 ° C. and a melting point of at most about 60 ° C. at atmospheric pressure. For example, esters of C ₈ to C ₂₂ fatty acids (particularly C ₁₂ to C ₁₈ fatty acids) (particularly C ₁ to C ₆ esters), for example methyl, ethyl or propyl laurate, myristate, palmitate, palmitole Acetates, linoleates, linolenolates, stearates or oleates, or mixtures thereof, for example esters having a total number of carbon atoms in the molecule of no more than 20, preferably esters of C ₁₂ to C ₁₈ fatty acids, Mineral oils, optionally hydrogenated vegetable oils, such as optionally hydrogenated cottonseed oil, linseed oil, mustard seed oil, neem oil, niger seed oils, for example methyl, ethyl or propyl laurate, or mixtures thereof oil), oistica oil, olive oil, palm oil, palm kernel oil, peanut oil, perilla oil, papy seed oil, grape seed oil, safflower oil, sesame oil or soybean oil.

The oil component may preferably also contain or be combined with one or more oil soluble surfactants, in particular it may be an oil that is self-emulsifying in water. Such surfactants may include one or more surfactants of relatively high HLB (hydrophilic-lipophilic balance) together with low HLB surfactants such as calcium stearate. Such oil solution components may be in the form commercially available as "grain oil" or "oil adjuvant". Typical oil components contain from about 99 to about 45, preferably from about 90 to about 60 parts by weight of oil, and from about 1 to about 55, preferably from about 10 to about 40 parts by weight of oil soluble surfactant. If water is present in soluble form or in a colloidal emulsion or microemulsion, the oil soluble surfactant can be partitioned (or present at the interface) between the oil phase and the aqueous phase.

The liquid saccharide solution may be monosaccharide, oligosaccharide or polysaccharide, or mixtures thereof, and the saccharide may be linear, branched or cyclic in nature. Such solvents for liquid saccharide solutions may be water, propylene glycol or glycerol, or any combination thereof. Liquid saccharide solutions are commonly referred to as syrups. Polysaccharides are generally known as dextrins, while oligosaccharides present in solution are known as maltodextrins. Among the liquid saccharide solutions, the compounds of particular use of the present invention include compounds described by HFCS, corn syrup, corn sweeteners, invert sugar, invert sugar syrup, sugars, sugar syrups and maltodextrins, and mixtures thereof, The liquid sugar solution is homogeneous and stable for at least 24 hours and contains up to about 75 parts by weight of water, preferably about 15 to about 50 parts by weight of water.

It is preferred when the saccharide is an oligosaccharide of the formula (C ₆ H ₁₂ O ₆ ) _n- (H ₂ O) _n-1 , wherein n is 1 or more and 50 or less. In particular, the sugars may have an average value of n of 1 to 5 in general. Particularly useful substances of this type are those in which n has an average value of about 1, the sugars are monosaccharides and the monosaccharides are keto-sugars, most preferably fructose. Fructose is marketed as HFCS, and the material represented, for example, by IsoClear 55 from Cargill can be used satisfactorily.

Non-ionic surfactants can be any that will make the combination stable and homogenous for at least 24 hours after they are formed.

Preferred non-ionic surfactants are the surfactants of formula (I) or (II) below.

_{^{R 1 · O · A n R}} 2

_{^{R 3 · N · (A n}} R 2) 2

In the formula,

R ¹ is a hydrocarbyl, hydrocarbonyl or hydrocarbamidyl group, glycerol or polyglycerol group suitably containing 6 to 24, preferably 8 to 22, in particular 12 to 18 carbon atoms, or sorbitan Or a sorbitol group;

A is a polyalkylene oxide unit containing an average of n alkylene oxide groups or mixed alkylene oxide groups, each of which has 2 to 8, preferably 2 or 3 carbon atoms;

n is 0 to 40, preferably 2 to 30, most preferably 5 to 20;

R ² is hydrogen or a hydrocarbonyl group having 8 to 22 carbon atoms, or a polycarboxylic acid group having 2 to 6 carbon atoms, such as maleate, fumarate, maleate, succinate or citrate, or Oligomers;

R ³ is a hydrocarbyl or hydrocarbonyl group having 8 to 22, preferably 12 to 18 carbon atoms.

Surfactant hydrocarbyl saccharides can be any that will produce a stable and homogeneous composition for at least 24 hours after being prepared.

Surfactant hydrocarbyl saccharides may be monoglycosides or polyglycosides or mixtures thereof. Hydrocarbyl saccharide surfactants are commonly referred to as hydrocarbyl polysaccharides even though the saccharide group contains only one sugar unit. Typically, such surfactants are mixtures of compounds having monosaccharides and polysaccharide (including disaccharide) units. Among the glycosides, the compounds specifically used in the present invention include compounds of the formula A and mixtures thereof.

ROG _a

Where

R is a hydrophobic moiety,

G is a sugar group,

a has an average value of 1 or more.

The R group can be an optionally substituted hydrocarbonyl group. In particular, R can be an alkyl, cycloalkyl, aryl, alkaryl, aralkyl or alkenyl group, preferably an alkyl group. The R group suitably contains 4 to 30 carbon atoms, preferably up to 24 carbon atoms, more preferably 6 to 18 carbon atoms, in particular 8 to 14 carbon atoms. Thus, R may, for example, be a mixture of alkyl or alkoxy groups containing, for example, 8 to 14 carbon atoms.

The sugar group G can be derived from one or more of fructose, glucose, mannose, galactose, telose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and ribose or mixtures thereof. The G group is conveniently derived from a glucose unit, in which case the glycoside is glucoside. When derived from sucrose, the group will include fructose and glucose groups.

a value is degree of polymerization. This value typically has an average value of at least 1.1, preferably at least 1.2, in particular at least 1.3. The a value is typically 8 or less, preferably 4 or less, for example 2 or less. If the glycoside is an alkyl glucoside, the a value is conveniently 1 to 2.

Preferred results are obtained when the glycoside is an alkyl polyglucoside of formula (B).

C _n H _{(2n + 1)} O (C ₆ H ₁₀ O ₅ ) _b H

Wherein n is 8 to 14,

b is greater than 1 and less than or equal to 2.

In particular, the glucoside may have an average value of n of 9 to 13, in particular about 10. The b value is typically at least 1.3 and at most 1.9. Particularly useful materials of this kind are those in which n is 8 to 11, has an average value of 10, and b is about 1.35. Surfactant hydrocarbyl sugars are commercially available and are commercially available, for example, under the names Atplus 452 and Atplus 438 from Uniqema, or under the trade name Triton from Dow Chemicals. Triton) The material sold as BG 10 can be used satisfactorily.

The anionic surfactant (s) can be any that will produce a stable and homogeneous composition for at least 24 hours after it is prepared. It is characterized by at least one anionic surfactant compound having the general formula (I ') or (II').

R ¹ -O-A _n -X

R ¹ -X

Where

R ¹ is a hydrocarbyl group having 6 to 24 carbon atoms, preferably 8 to 22 carbon atoms, most preferably 12 to 18 carbon atoms,

A is a polyalkylene oxide unit containing an average of n alkylene oxide groups or mixed alkylene oxide groups, wherein each alkylene group has from 2 to 8, preferably 2 or 3 carbon atoms Have,

n is 0 to 60, preferably 2 to 30, most preferably 3 to 15,

X is a group comprising at least one acidic H atom or a salt thereof, preferably an amine salt.

Wherein X is a group comprising one or more acidic atoms or salts thereof, which means that the X groups can be ionized in an aqueous medium to form anionic groups. Thus, this group renders the surfactant anionic by providing an anionic functional group. Such functional groups may be some or all oxidized phosphorus, sulfur or carbon acid groups.

The other nonionic surfactant (s) can be any that will produce a stable and homogeneous composition for at least 24 hours after it is prepared.

Particularly preferred results are obtained when the nonionic surfactant is of formula (I) or (II).

<Formula I>

_{^{R 1 · O · A n R}} 2

<Formula II>

_{^{R 3 · N · (A n}} R 2) 2

Where

R ¹ is a hydrocarbyl, hydrocarbonyl or hydrocarbamidyl group, glycerol or polyglycerol group suitably containing 6 to 24, preferably 8 to 22, in particular 12 to 18 carbon atoms, or sorbitan Or a sorbitol group,

A is a polyalkylene oxide unit containing an average of n alkylene oxide groups or mixed alkylene oxide groups, wherein each alkylene group has from 2 to 8, preferably 2 or 3 carbon atoms ,

n is 0 to 40, preferably 2 to 30, most preferably 5 to 20,

R ² is hydrogen or a hydrocarbonyl group having 8 to 22 carbon atoms, or a polycarboxylic acid group having 2 to 6 carbon atoms, for example maleate, fumarate, maleate, succinate or citrate, or Oligomers thereof,

R ³ is a hydrocarbyl or hydrocarbonyl group having 8 to 22, preferably 12 to 18 carbon atoms.

The relative proportions (weight ratios) of the oil component (a), the liquid saccharide solution (b) and the nonionic surfactant (c) are suitably

a) 10 to 90, in particular 25 to 75, preferably 30 to 60,

b) 10 to 90, in particular 15 to 45, preferably 20 to 40, and

c) 5 to 80, in particular 5 to 60, preferably 10 to 45,

The proportion of the optional one or more surfactant hydrocarbyl sugars (d), or anionic surfactants (e), or nonionic surfactants (f)

d) 1 to 20, in particular 2 to 15, preferably 3 to 10, or

e) 1 to 20, in particular 2 to 15, preferably 3 to 10, or

f) from 1 to 20, in particular from 2 to 15, preferably from 3 to 10.

Any chemical agent specific to the intended use of the composition will be a pesticide. Pesticides are typically one or more nutrients, growth regulators, herbicides and / or insect repellents such as insecticides, fungicides or tick repellents.

The present invention includes a method of making a composition of the present invention comprising mixing the components together.

The present invention also encompasses a diluted formulation comprising about 10 to about 10,000 times the weight of this composition together with a composition comprising components (a), (b) and (c) according to the invention. The concentrated compositions of the present invention are readily emulsified upon dilution in water to form a formulation. At a relatively low level of dilution, the product will be an oil-in-water emulsion having a relatively high concentration of oil. This intermediate emulsion may then be further diluted with an aqueous solution or suspension of water or other components desired for the final formulation.

Diluted formulations can be prepared in a variety of ways. That is, a formulation comprising components (a), (b), (c) and optionally one or more of components (d), (e) or (f) and water may contain components (a), (b), ( The composition of c) and optionally one or more of components (d), (e) or (f) can be prepared by simple mixing with water.

In another aspect, the invention provides a method of applying the formulation of the invention to a substrate. Embodiments of this method include a method of treating vegetation by applying said formulation according to the invention to plants and / or soil, comprising certain chemical agents which are pesticides.

In this embodiment, the pesticide may be one or more growth regulators, herbicides, and / or insect repellents, for example insecticides, fungicides or tick repellents. Thus embodiments of the methods of the invention wherein the formulations are applied include methods for killing or inhibiting vegetation by applying formulations comprising special chemicals that are one or more growth regulators and / or herbicides, and one or more insect repellents, eg Methods of killing or inhibiting plant pests by applying agents comprising special chemicals, for example insecticides, fungicides or tick repellents.

In this embodiment, the effect of the pesticide, which is one or more growth regulators, herbicides, and / or insecticides, for example insecticides, fungicides, or tick insecticides, is characterized by the presence of oil components and / or sugars and / or interfaces present in the composition. Increased by the active agent composition.

Examples of pesticides which are typically one or more growth regulators, herbicides, and / or insecticides, for example insecticides, fungicides or tick insecticides, in particular growth regulators, herbicides and the like are phosphonomethyl-n-carboxymethyl (PMCM) compounds and And related compounds of formula (C)

R ⁷ C (O) CH ₂ N (Z) CH ₂ P (O) (R ⁷ ) ₂

Wherein each R ⁷ is independently halogen, —NHOH, —N (R ⁸ ) ₂ , —OR ⁹ , —SR ⁹ or —OM, and R ⁸ is independently hydrogen, or preferably less than about 5 Alkyl or hydroxyalkyl containing carbon atoms of, preferably alkenyl containing less than about 5 carbon atoms, or phenyl; Each R ⁹ is independently hydrogen, alkyl, preferably hydroxyalkyl or chloroalkyl containing less than about 5 carbon atoms, preferably alkoxy containing less than about 5 carbon atoms, preferably about Alkylene amines, phenyl or benzyl containing less than 12 carbon atoms; M is hydrogen or an agriculturally acceptable salt forming residue such as an alkali metal, alkaline earth metal, tin, ammonium, organic ammonium, alkyl sulfonium, alkyl sulfoxium, alkyl phosphonium residue or combinations thereof; Z is hydrogen, an organic residue or an inorganic residue.

Representative patents that disclose at least some of these compounds are described in U.S. Patents 3799758, 4397676, 4140513, 4315765, 3868407, 4455131, 4481026, 4414158, 4120689, 4472189, 4341549 and 3948975. Patents that disclose PMCM compounds in which Z is other than hydrogen include US Pat. Nos. 3,887,915, 3933946, 4060299, 4119430, 4322239, and 4084954.

In preferred PMCM compounds,

Z is hydrogen or an organic substituent;

R ⁹ is independently hydrogen, alkyl, preferably hydroxyalkyl or chloroalkyl containing less than about 5 carbon atoms, preferably alkoxy containing less than about 5 carbon atoms, preferably about 12 Selected from alkylene amines, phenyl or benzyl moieties containing less than carbon atoms;

M is selected from hydrogen and agriculturally acceptable salt forming residues, alkali metals, phosphonium residues or combinations thereof.

Representative patents that disclose at least some of these compounds are described in U.S. Patents 3799758, 4397676, 4140513, 4315765, 3868407, 4454531, 4481026, 4414158, 4120689, 4472189, 4341549 and 3948975. Patents that disclose PMCM compounds in which Z is other than hydrogen include US Pat. Nos. 3,887,915, 3933946, 4060299, 4119430, 4322239, and 4084954.

In preferred PMCM compounds, Z is hydrogen or an organic substituent such as methylene carboxyl; Methylene phosphone; And methylene cyano. Other organic substituents include carboxyl such as formyl, acetyl, benzoyl, perfluoroacyl and thiocarbonyl; Ethylene such as cyano, carbamoyl or carboxy substituted ethyl; And benzene sulfonyl substituents. Patents that disclose compounds in which nitrogen has three organic substituents are described in U.S. Pat.Nos. 3,565,753,355,676,393,530,3970695,3988142,3991095,3996040,4047927,4180394 US Pat. Nos. 4,033,756,4261727 and 4312662. Preferred tertiary nitrogen substituted PMCM compounds are N, N-bis (phosphonomethyl) glycine.

Most preferred are those PMCM compounds in which Z is hydrogen when the required plant activity is herbicidal activity.

The patents listed above are incorporated herein by reference.

Illustrative examples of agriculturally acceptable salt forming moieties represented by M as in OM include alkali metals having an atomic weight of 22 to 133, such as sodium, potassium, or rubidium; Alkaline earth metals having an atomic weight of 24 to 88, such as magnesium or calcium; Ammonium and aliphatic ammonium (aliphatic is primary, secondary, tertiary or quaternary and preferably the total number of carbon atoms does not exceed about 12); Phenylammonium; Preferably trialkylsulfonium in which the total number of carbons in the three alkyl substituents does not exceed about 6, such as trimethylsulfonium, ethyl dimethylsulfonium, propyl dimethylsulfonium and the like; Preferably trialkylsulfoniums in which the total number of carbons in the three alkyl substituents does not exceed about 6, such as trimethylsulfonium, ethyl dimethylsulfonium, propyl dimethylsulfonium and the like; Tetraalkylphosphoniums such as tetramethylphosphonium, ethyl trimethylphosphonium, propyltrimethylphosphonium and similar groups.

In a preferred composition according to the invention, M is independently selected from the agriculturally acceptable salt forming moieties and hydrogen described above. In a more preferred composition, M is an alkali metal, ammonium, monoalkyl ammonium or trialkylsulfonium moiety. In a particularly preferred composition, only one M is an alkali metal, ammonium, monoalkyl ammonium, or trialkylsulfonium moiety, while the two Ms are hydrogen.

Particularly preferred compositions include isopropylamine N-phosphonomethylglycine, trimethylsulfonium N-phosphonomethylglycine and sodium sesqui-N-phosphonomethylglycine. Combinations of two or more PMCM compounds can be applied in the composition formulations and methods of the present invention.

The following examples illustrate the invention. All quantities are by weight unless otherwise indicated.

Example 1

The following concentrates were prepared.

Ingredient code Ingredient Name weight

a mineral oil 44.12

b High fructose corn syrup solution 29.41

c ethoxylated tallowamine 26.47

The concentrate was self-emulsified with 5% dilution in water. If 0.5% by volume of pesticide glyphosate was introduced into the concentrate prior to dilution in water, the diluted composition was effective as a herbicide.

Example 2

The following concentrates were prepared.

Ingredient code Ingredient Name weight

a mineral oil 46.15

b High fructose corn syrup solution 15.38

c ethoxylated tallowamine 30.77

d C ₉ -C ₁₁ Alkylpolysaccharide 7.69

The concentrate was self-emulsified with 5% dilution in water. If 0.5% by volume of pesticide glyphosate was introduced into the concentrate prior to dilution in water, the diluted composition was effective as a herbicide.

Example 3

The following concentrates were prepared.

Ingredient code Ingredient Name weight

a mineral oil 45.45

b High fructose corn syrup solution 18.16

c ethoxylated tallowamine 30.30

e dodecylbenzenesulfonate, isopropylamine salt 6.06

The concentrate was self-emulsified with 5% dilution in water. If 0.5% by volume of pesticide glyphosate was introduced into the concentrate prior to dilution in water, the diluted composition was effective as a herbicide.

Example 4

The following concentrates were prepared.

Ingredient code Ingredient Name weight

a mineral oil 42.55

b High fructose corn syrup solution 25.55

c ethoxylated tallowamine 28.37

f sorbitan monooleate 3.55

The concentrate was self-emulsified with 5% dilution in water. If 0.5% by volume of pesticide glyphosate was introduced into the concentrate prior to dilution in water, the diluted composition was effective as a herbicide.

Example 5

The following concentrates were prepared.

Ingredient code Ingredient Name weight

a mineral oil 44.12

b High fructose corn syrup solution 14.71

c ethoxylated tallowamine 29.41

d C ₉ -C ₁₁ Alkylpolysaccharide 8.82

f mono- and di-glycerides 2.94

The concentrate was self-emulsified with 5% dilution in water. If 0.5% by volume of pesticide glyphosate was introduced into the concentrate prior to dilution in water, the diluted composition was effective as a herbicide.

Example 6

The following concentrates were prepared.

Ingredient code Ingredient Name weight

a mineral oil 43.17

b High fructose corn syrup solution 18.71

c ethoxylated tallowamine 28.78

e dodecylbenzenesulfonate, isopropylamine salt 7.19

f sorbitan monooleate 2.16

The concentrate was self-emulsified with 5% dilution in water. If 0.5% by volume of pesticide glyphosate was introduced into the concentrate prior to dilution in water, the diluted composition was effective as a herbicide.

Example 7

The following concentrates were prepared.

Ingredient code Ingredient Name weight

a mineral oil 33.78

b High fructose corn syrup solution 14.93

c ethoxylated tallowamine 29.85

d C ₉ -C ₁₁ Alkylpolysaccharide 7.46

e dodecylbenzenesulfonate, isopropylamine salt 2.99

The concentrate was self-emulsified with 5% dilution in water. If 0.5% by volume of pesticide glyphosate was introduced into the concentrate prior to dilution in water, the diluted composition was effective as a herbicide.

Example 8

The following concentrates were prepared.

Ingredient code Ingredient Name weight

a mineral oil 37.97

b High fructose corn syrup solution 25.32

c ethoxylated tallowamine 25.32

d C ₉ -C ₁₁ Alkylpolysaccharide 6.33

e dodecylbenzenesulfonate, isopropylamine salt 2.53

f sorbitan monooleate 2.53

The concentrate was self-emulsified with 5% dilution in water. If 0.5% by volume of pesticide glyphosate was introduced into the concentrate prior to dilution in water, the diluted composition was effective as a herbicide.

Those skilled in the art will appreciate that the invention may be practiced by other than the above described embodiments which are presented for purposes of illustration but not limitation.

Claims (23)

a) 25 to 75 parts by weight of one or more oil components; b) 15 to 45 parts by weight of one or more non-surfactant sugars present in solution; And c) 5 to 45 parts by weight of at least one nonionic surfactant having formula (I) or (II) And at least one of the following additional ingredients: d) 1 to 20 parts by weight of one or more surfactant hydrocarbyl sugars; or e) 1 to 20 parts by weight of one or more anionic surfactants; or f) 1 to 20 parts by weight of one or more additional nonionic surfactants A homogeneous agrochemical concentrated composition based on self-emulsifying oil, further comprising 10 to 50% by weight of total surfactant. <Formula I> R ¹ · A _n R ² <Formula II> _{^{R 3 · N · (A n}} R 2) 2 In the formula, R ¹ is a hydrocarbyl, hydrocarbonyl or hydrocarbamidyl group, glycerol or polyglycerol group having 6 to 24 carbon atoms, or a sorbitan or sorbitol group; A is a polyalkylene oxide unit containing an average of n alkylene oxide groups or mixed alkylene oxide groups, wherein the alkylene groups each have 2 to 8 carbon atoms; n is 0 to 40; R ² is hydrogen or a hydrocarbonyl group having 8 to 22 carbon atoms, or a polycarboxylic acid group having 2 to 6 carbon atoms; R ³ is a hydrocarbyl or hydrocarbonyl group having 8 to 22 carbon atoms. The composition of claim 1 wherein each of the components d), e) and f) is present. The composition according to claim 1 or 2, wherein the relative weight ratio of component a) oil in the concentrated composition is 30 to 60 parts by weight. The process of claim 1 or 2, wherein at least one component d), e) or f) in the concentrated composition is: d) 2 to 15 parts by weight, e) 2 to 15 parts by weight, f) 2 to 15 parts by weight A composition present in an amount of. 3. The composition of claim 1, wherein said oil component a) is selected to have a boiling point of greater than 200 ° C. 4. The composition of claim 1, wherein said oil component a) comprises mineral oil, vegetable oil, ester of C ₈ -C ₂₂ fatty acids, or mixtures of more than one thereof. The composition of claim 1, wherein said non-surfactant saccharide b) is at least one of monosaccharides, oligosaccharides and / or polysaccharides. The method of claim 1, wherein the nonionic surfactant c) is an alkoxylated fatty acid, polyalkylene glycol ester, alkoxylated glyceride, alkoxylated sorbitan and / or sorbitol ester, alkylphenol alkoxylate, alcohol alkoxylate, alkyl At least one of amine alkoxylates, alkanolamides and / or alkoxylated alkanolamides. The composition of claim 1 wherein at least one alkyl polysaccharide component d) is present in formula A: <Formula A> ROG _a In the formula, R is a hydrophobic moiety; G is a sugar group; a has an average value of 1 or more. 10. The compound of claim 9, wherein component d) is present as an alkyl polyglucoside of formula B, and when at least one anionic surfactant component e) is present, is formula I 'or II' and at least one additional When the nonionic surfactant component f) is present. <Formula B> C _n H _{(2n + 1)} O (C ₆ H ₁₀ O ₅ ) _b H In formula, n is 8-14, b is 1 or more and less than 3. <Formula I ' R ¹ -O-A _n -X <Formula II '> R ¹ -X In the formula, R ¹ is a hydrocarbyl group having 6 to 24 carbon atoms; A is a polyalkylene oxide unit containing an average of n alkylene oxide groups or mixed alkylene oxide groups, wherein the alkylene groups each have 2 to 8 carbon atoms; n is 0 to 60; X is a group or salt thereof containing at least one acidic H atom. <Formula I> R ¹ · A _n R ² <Formula II> _{^{R 3 · N · (A n}} R 2) 2 In the formula, R ¹ is a hydrocarbyl, hydrocarbonyl or hydrocarbamidyl group, glycerol or polyglycerol group having 6 to 24 carbon atoms, or a sorbitan or sorbitol group; A is a polyalkylene oxide unit containing an average of n alkylene oxide groups or mixed alkylene oxide groups, wherein the alkylene groups each have 2 to 8 carbon atoms; n is 0 to 40; R ² is hydrogen or a hydrocarbonyl group having 8 to 22 carbon atoms, or a polycarboxylic acid group having 2 to 6 carbon atoms; R ³ is a hydrocarbyl or hydrocarbonyl group having 8 to 22 carbon atoms. The composition of claim 10 wherein component e) is alkyl carboxylate and / or alkyl ether carboxylate, alkyl sulfate and / or alkyl or alkylphenyl ether sulfate, alkyl or alkylphenyl phosphate and / or alkyl or alkylphenyl ether At least one of phosphate, alkyl or alkylphenyl sulfosuccinate and / or alkyl or alkylphenyl ether sulfosuccinate, alkyl or alkylphenyl sulfonate, and / or alkyl or alkylphenyl phosphonate. The composition of claim 10 wherein component f) is at least one of glycerol or polyglycerol esters, sorbitol or sorbitan esters, ethylene or propylene glycol esters, polyethylene glycol esters and / or fatty alcohols. A method of forming a diluted pesticide formulation comprising diluting the composition of claim 1 or 2 in water to emulsify and further comprising the pesticide in the diluted formulation. The method of claim 13, wherein the pesticide is a selective or non-selective herbicide. The method of claim 13, wherein the pesticide is one or more of growth regulators, herbicides, and / or pesticides. The method of claim 13, wherein the amount of water used to dilute the concentrate is 10 to 10,000 times the weight of the concentrated composition. 15. The method of claim 14, wherein the pesticide is at least one phosphonomethyl-N-carboxymethyl herbicide of the formula: R ¹ C (O) CH ₂ N (Z) CH ₂ P (O) (R ¹ ) ₂ In the formula, Each R ¹ is independently halogen, -NHOH, -N (R ² ) ₂ , -OR ³ , -SR ³ or -OM, R ² is independently hydrogen or alkyl or hydroxyalkyl, alkenyl or phenyl; Each R ³ is independently hydrogen, alkyl, hydroxyalkyl or chloroalkyl, alkoxy, alkylene amine, phenyl or benzyl; M is hydrogen or an agriculturally acceptable salt forming moiety; Z is hydrogen, an organic residue or an inorganic residue. A vegetation treatment method comprising applying to a plant and / or soil a diluted pesticide formulation prepared as claimed in claim 13. 19. The method of claim 18, wherein the pesticide is at least one phosphonomethyl-N-carboxymethyl herbicide of the formula: R ¹ C (O) CH ₂ N (Z) CH ₂ P (O) (R ¹ ) ₂ In the formula, Each R ¹ is independently halogen, -NHOH, -N (R ² ) ₂ , -OR ³ , -SR ³ or -OM, R ² is independently hydrogen or alkyl or hydroxyalkyl, alkenyl or phenyl; Each R ³ is independently hydrogen, alkyl, hydroxyalkyl or chloroalkyl, alkoxy, alkylene amine, phenyl or benzyl; M is hydrogen or an agriculturally acceptable salt forming moiety; Z is hydrogen, an organic residue or an inorganic residue. delete delete delete delete